Benzodioxanones and organoleptic uses thereof

ABSTRACT

Described are the bicyclic compounds having the generic structure: ##STR1## wherein Z is benzo or cyclohexano and processes for preparing same and compositions containing same for use in augmenting or enhancing the aroma and/or taste of foodstuffs, chewing gums, toothpastes and medicinal products; tobacco; perfumes, colognes and perfumed articles, produced by a process described by the reaction: ##STR2## wherein X is chloro or bromo; Y is chloro, bromo or OR; R is C 1  -C 3  lower alkyl, that is: methyl, ethyl, n-propyl or i-propyl; B is MOH, MH, MOR&#39;, trialkylamine, or M 2  --CO 3  (wherein M is alkali metal such as sodium or potassium); and R&#39; is C 1  -C 5  lower alkyl, such as methyl, ethyl, n-propyl, i-propyl and t-butyl with the proviso that B is trialkylamine or an alkali metal carbonate when Y is chloro or bromo and B is MOH, MH or MOR&#39; when Y is OR. 
     The above mentioned compounds produce: 
     A. In foodstuffs, chewing gums and medicinal products, a sweet, green, fruity, coumarinic, marzipan-like aroma and taste. 
     B. In tobacco, a sweet, spicy, vanilla-like, woody, hay, tobacco-like aroma prior to smoking and a sweet, spicy, hay, tobacco-like aroma on smoking. 
     C. In perfumes, colognes and perfumed articles, sweet, fruity, and green aroma nuances.

This is a divisional of application Ser. No. 075,071, filed Sept. 13,1979 now U.S. Pat. No. 4,241,097.

BACKGROUND OF THE INVENTION

The present invention relates to bicyclic compounds having the genericstructure: ##STR3## wherein Z is cyclohexano or benzo and novelcompositions using such cyclic compounds to augment or enhance theflavor and/or aroma of consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (augment or enhance) flavors and fragrances to (orin) various consumable materials. These substances are used to diminishthe use of natural materials some of which may be in short supply and toprovide more uniform properties in the finished product.

Sweet, green, fruity, coumarinic, marzipan-like aromas and tastes areparticularly desirable for many uses in foodstuff, chewing gum,toothpaste and medicinal product flavors. Sweet, spicy, vanilla-like,woody, hay, tobacco-like aromas prior to smoking and sweet, spicy, hay,tobacco-like aromas on smoking are desirable in tobacco and tobaccoflavor compositions especially where these notes appear both in themainstream and the sidestream on smoking as well as prior to smoking.Sweet, fruity, and green aroma nuances are especially desirable inseveral types of perfume compositions, perfumed articles e.g., anionic,cationic and nonionic solid or liquid detergents and colognes.

The foregoing organoleptic properties have heretofore been provided bycoumarin or homologues or analogs thereof having the structures:##STR4##

Coumarin, 1,2-benzopyrone having the structure: ##STR5## is described in"Perfume and Flavor Chemicals (Aroma Chemicals)" by Stephen Arctander,1969 (Monograph 704) as being extensively used in perfumery to supportherbaceous odors, lavender, lavandin, rosemary, citrus oils, oakmossetc., and as a fixative in numerous types of fragrances. Arctanderstates that coumarin is almost a standard ingredient in Fougere typeswith amyl salicylate and lavender notes with or without Oakmoss.Arctander states that coumarin is not permitted for food use in theUnited States of America and is also banned from food flavorings in anumber of other countries. Arctander further states that the hazardouslevel of coumarin is estimated at 3 grams per day for adult humanbeings. Accordingly, it has been found necessary in the flavor andfragrance industry to find a suitable replacement for coumarin.

Thus, the compounds of the instant case having the generic structure:##STR6## wherein Z is benzo or cyclohexano which generic structureincludes the structures: ##STR7## were designed as analogs for 6-methylcoumarin, 7-methyl coumarin and coumarin itself, having the structures:##STR8## However, these coumarin derivatives have been indicated to havedisplayed photosensitization in toxicological testing and it is thereforbeen ascertained to be prudent to replace same.

Other known coumarin analogs do exist having the structures: ##STR9##however, these analogs are so expensive that it is not possible toproduce them as replacements for coumarin.

The compound having the generic structure: ##STR10## is an inexpensivereplacement which is produced using readily available startingmaterials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the NMR spectrum for the compound produced according toExample I having the structure: ##STR11##

FIG. 2 is the infrared spectrum for the compound produced according toExample I having the structure: ##STR12##

FIG. 3 is the NMR spectrum for the compound produced according toExample III having the structure: ##STR13##

FIG. 4 is the infrared spectrum for the compound prepared according tothe process of Example III having the structure: ##STR14##

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, toothpaste and medicinal products and flavoringcompositions having a sweet, green, fruity, coumarinic, marzipan-likearoma and taste characteristics; novel perfume compositions, perfumedarticles (such as anionic, cationic, and nonionic solid and liquiddetergents, disposable fabric softener articles and cosmetic powders)and colognes having sweet, fruity, and green aroma nuances, as well asnovel smoking tobaccos and smoking tobacco flavoring compositions havingsweet, spicy, vanilla-like, woody, hay, tobacco-like aromas prior tosmoking and sweet, spicy, hay, tobacco-like aromas on smoking may beprovided by the utilization of bicyclic compounds having the structure:##STR15## wherein Z is benzo or cyclohexano.

The generic structure: ##STR16## is intended herein to cover compoundshaving the structure: ##STR17## wherein the structures: ##STR18## are,respectively, the "trans" and "cis" isomers of the compound having thegeneric structure: ##STR19##

Because of their organoleptic properties and their low cost ofmanufacture as well as their excellent toxicological properties, thecompounds defined according to the structure: ##STR20## have unique,unexpected and advantageous properties over coumarin and its analogs andhomologues having the structures: ##STR21##

The compounds having the structure defined according to the genus:##STR22## wherein Z is benzo or cyclohexano useful as indicated, supra,may be produced by processes defined according to the reaction scheme:##STR23## wherein X is chloro or bromo; Y is chloro, bromo or --OR; withR being C₁ -C₃ lower alkyl such as methyl, ethyl, n-propyl or i-propyl;where B is MOH; MH; MOR'; a trialkylamine or M₂ --CO₃ with M being analkali metal such as sodium or potassium and R' being C₁ -C₅ alkyl suchas methyl, ethyl, i-propyl, n-propyl or t-butyl with the proviso that Bis trialkylamine or M₂ --CO₃ when Y is Cl or Br and B is MOH, MH, orMOR' when Y is --OR. The foregoing generic reaction scheme isexemplified by the following three specific reaction schemes: ##STR24##

Concerning the reaction Scheme I, to wit: ##STR25## it is preferred touse chloroacetyl chloride or bromoacetyl bromide in the presence of anon-nucleophilic base such as a tertiary amine such as triethylamine oran alkali metal carbonate such as sodium carbonate. It is preferred thatthe mole ratio of haloacetylhalide:base be about 1:2 and that the moleration of catechol:haloacetylhalide be about 1:1. The reaction should becarried out in a solvent such as tetrahydrofuran, toluene, diethyletheror chloroform each of which is inert to the reaction mass. The reactiontemperature may vary from about 40° C. up to the reflux temperature ofthe solvent at the pressure at which the reaction is carried out. Thepressure that the reaction may be carried out may vary from 0.5atmospheres up to 20 atmospheres with a pressure of 1 atmosphere beingpreferred. Thus, higher pressures do not give rise to any increase inyield and give rise to a more expensive process in view of the moreexpensive equipment that must be utilized.

Insofar as Reaction Scheme II, to wit, involving the two reactions:##STR26## it is preferred that the phase transfer agent be used alongwith the base which may be any alkali metal hydroxide, e.g. LiOH, NaOHor KOH. The phase transfer agent may be any of those described in U.S.Pat. No. 4,010,207, issued on Mar. 1, 1977, for example, Aliquat® 336 (abrand of tricapryl methyl ammonium chloride produced by the GeneralMills Chemical Company of Minneapolis, Minn.). It is preferred that thealkylhaloacetate used be either ethyl chloroacetate or ethylbromoacetate. It is preferred that the concentration of phase transferagent be from 5 up to 20 grams of phase transfer agent per mole ofalkali metal hydroxide. Furthermore, it is preferred that an inertsolvent be used in the reaction such as toluene or chloroform.

Insofar as Reaction Scheme III is concerned, that is wherein thereaction exemplified by the following sequence is carried out: ##STR27##the NaH may be replaced by any alkali metal hydride such as KH or LiH aswell as an alkali metal alkoxide such as sodium methylate or an alkalimetal butoxide such as potassium t-butoxide. Insofar as the first stepof the reaction is concerned, the reaction is carried out using an inertsolvent such as tetrahydrofuran, xylene, benzene or diethylether.Insofar as the second part of this reaction sequence is concerned, it ispreferred that the mole ratio of cathechol salt:alkylhaloacetate beabout 1:1 and it is preferred that the reaction be carried out in aninert solvent such as toluene, benzene, xylene, chloroform ordiethylether at a temperature of from about 40° C. up to about reflux;preferably at a temperature of about 80° C.

The compound having the generic structure: ##STR28## hereinafterreferred to as the "cyclic chemical compounds" of our invention arecapable of supplying and/or potentiating certain flavor and aroma notesusually lacking in many fruit flavors as well as tobacco flavorsheretofore. Furthermore, the cyclic chemical compounds of our inventionare capable of supplying certain fragrance notes usually lacking in manyperfumery materials, for example, Fougere formulations, lavendinformulations, citrusy formulations, and oakmoss type formulations. Inaddition these materials are capable of acting as fixatives in perfumerywhile augmenting or enhancing certain aroma nuances in themselves.

When the cyclic chemical compounds of our invention are used asfoodstuff flavor adjuvants the nature of the co-ingredients includedwith said cyclic chemical compounds in formulating the productcomposition will also serve to alter, augment or enhance theorganoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs includes soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "medicinal products" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, and chewable medicinal tablets.

The term "chewing gum" is intended herein to be a foodstuff compositioncomprising a substantially water-insoluble, chewable plastic gum basesuch as chicle, or substitutes therefor, including jelutong, guttakayrubber or certain comestible natural or synthetic resins or waxes.Incorporated with the gum base in admixture therewith may beplasticizers or softening agents, e.g., glycerine; and a flavoringcomposition which incorporates one or more of the cyclic chemicalcompounds of our invention, and, in addition, sweetening agents whichmay be sugars, including sucrose or dextrose and/or artificialsweeteners such as cyclamates or saccharin. Other optional ingredientsmay be present.

The term "augment" in its various forms is used herein to mean thesupplying, modifying or imparting of a flavor or aroma characteristic,note or nuance to an otherwise bland, relatively tasteless ornon-odorous substance or modifying an existing flavor or aromacharacteristic where the natural flavor is deficient in some regard, orsupplementing the existing flavor or aroma impression to modify itsquality, character, taste or aroma.

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note or nuance.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is required that any suchmaterial be "ingestibly acceptable", and thus non-toxic or otherwisenon-deleterious, particularly from an organoleptic standpoint wherebythe ultimate flavor and/or aroma of the consumable material used doesnot cause the consumable material to have unacceptable aroma and tastenuances.

It is a further requirement that such material be organolepticallycompatible with the foodstuff with which it is used so that the flavorand aroma nuances of such material, taken together with the flavor andaroma nuances of the foodstuff (as a whole) give rise to a harmoniouslyaesthetically pleasing aroma and taste profile. Such material, ingeneral, may be characterized as flavoring adjuvants or vehiclescomprising broadly, stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., critic acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids,cabohydrates; starches, pectins, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcumin and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium glyconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-cis-3-pentenoic acid; ketonesand aldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl,beta,beta-dimethyl-acrolein, n-hexanal, 2- hexenal, cis-3-hexenal,2-heptenal, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,2-methyl-3-butanone, 2-pentanone, 2-pentenal and propanal; alcohols suchas 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol,geraniol, 1-hexanol, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol,3-methyl-3-buten-1-ol, 1-pentenol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate; esters, suchas butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate,ethyl butyrate, ethyl caproate, ethyl cinnamate, ethyl crotonate, ethylformate, ethyl isobutyrate, ethyl isovalerate, ethylalpha-methyl-butyrate, ethyl propionate, ethyl salicylate,trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, hexylbutyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methylbutyrate, methyl caproate, methyl isobutyrate, methyl-2-methyl-butyrate,propyl acetate, amyl acetate, amyl butyrate, benzyl salicylate, dimethylanthranilate, ethyl methylphenyl-glycidate ethyl succinate isobutylcinnamate and terpenyl acetate; essential oils, such as jasmineabsolute, rose absolute, orris absolute, lemon essential oil, Bulgarianrose, yara yara, natural raspberry oil and vanilla; lactones, sulfides,e.g., methyl sulfide and other materials such as maltol, acetoin andacetals (e.g., 1,1-diethoxyethane,1,1-dimethoxyethane anddimethoxymethane.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,be capable of providing an environment in which the cyclic chemicalcompounds can be dispersed or admixed to provide a homogeneous medium.In addition, selection of one or more flavoring adjuvants, as well asthe quantities thereof will depend upon the precise organolepticcharacter desired in the finished product. Thus, in the case offlavoring compositions, ingredient selection will vary in accordancewith the foodstuff to which the flavor and aroma are to be imparted. Incontradistinction, in the preparation of solid products, e.g., simulatedfoodstuffs, ingredients capable of providing normally solid compositionsshould be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of cyclicchemical compound(s) employed in a particular instance can vary over arelatively wide range whereby its desired organoleptic effects (havingreference to the nature of the product) are achieved. Thus,correspondingly greater amounts would be necessary in those instanceswherein the ultimate food composition to be flavored is relatively blandto the taste, whereas relatively minor quantities may suffice forpurposes of enhancing the composition merely deficient in natural flavoror aroma. The primary requirement is that the amount selected, (to beeffective) be sufficient to augment or enhance the organolepticcharacteristics of the parent composition, (whether foodstuff per se orflavoring composition).

The use of insufficient quantities of cyclic chemical compounds will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities prove needlessly costly and in extremecases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, it is found thatquantities of cyclic chemical compounds ranging from a small buteffective amount, e.g., 0.5 parts per million up to about 20 parts permillion by weight based on total composition are suitable.Concentrations in excess of the maximum quantity stated are not normallyrecommended, since they fail to prove commensurate enhancement oforganoleptic properties. In those instances, wherein the cyclic chemicalcompounds are added to the foodstuff as an integral component of aflavoring composition, it is, of course, essential that the totalquantity of flavoring composition employed be sufficient to yield aneffective cyclic chemical compound concentration in the foodstuffproduct.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the cyclic chemical compound inconcentrations ranging from about 0.1% up to about 15% by weight basedon the total weight of said flavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing one or more of the cyclic chemicalcompounds of our invention with, for example, gum arabic, gumtragacanth, carrageenan and the like, and thereafter spray-drying theresultant mixture whereby to obtain the particular solid product.Pre-prepared flavor mixes in powder form, e.g., a fruit-flavoredpowdered mix are obtained by mixing the dried solid components, e.g.,starch, sugar and the like and cyclic chemical compounds in a dryblender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the cyclic chemical compoundsthe following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Vanillin;

Methyl cinnamate;

Ethyl pelargonate;

Methyl anthranilate;

Isoamyl acetate;

Isobutyl acetate;

Alpha ionone;

Ethyl butyrate;

Acetic acid;

Gamma-undecalactone;

1-(3-(methylthio)butyryl-2,6,6-trimethyl cyclohexene;

1(3(-methylthio)butyryl)-2,6,6-trimethyl-1,3-cyclohexadiene;

Naphthyl ethyl ether;

Diacetyl;

Ethyl acetate;

Anethole;

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

2-Methyl-cis-3-pentenoic acid;

Ethyl-2-methyl-cis-3-pentenoate;

Methyl-2-methyl-cis-3-pentenoate;

Elemencine (4-allyl-1,2,6-trimethoxy benzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxy benzene); and

2-(4-hydroxy-4-methylpentyl)norbornadiene prepared according to U.S.Pat. No. 3,886,289, issued on May 27, 1975.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor, as well asmethods of making the same which overcome specific problems heretoforeencountered in which specific desired sweet, spicy, vanilla-like, woody,hay, tobacco-like flavor and aroma characteristics are created orenhanced and may be readily controlled and maintained at the desireduniform level regardless of variations in the tobacco components of theblend.

This invention further provides improved tobacco additives and methodswhereby various desirable sweet, spicy, vanilla-like, woody, hay,tobacco-like flavor and aroma characteristics may be imparted to smokingtobacco products and may be readily varied and controlled to produce thedesired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient cyclicchemical compounds.

In addition to the cyclic chemical compounds of our invention, otherflavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in mixture with thecyclic chemical compounds as follows:

I. SYNTHETIC MATERIALS

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

β-Damascone;

β-Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethyl naphtho-(2,1-b-)-furan;

4-Hydroxy hexanoic acid, gamma lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372, issued on June 29, 1971

II. NATURAL OILS

Celery seed oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil;

An aroma and flavoring concentrate containing one or more of the cyclicchemical compounds of our invention and, if desired, one or more of theabove indicated additional flavoring additives may be added to thesmoking tobacco material, to the filter or to the leaf or paper wrapper.The smoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as the augmentation, or the enhancement or the imparting of thesweet, spicy, vanilla-like, woody, hay, tobacco-like notes areconcerned, we have found that satisfactory results are obtained if theproportion by weight of the sum total of cyclic chemical compounds tosmoking tobacco material is between 250 ppm and 1,500 ppm (0.025%-1.5%)of the active ingredients to the smoking tobacco material. We havefurther found that satisfactory results are obtained if the proportionby weight of the sum total of cyclic chemical compounds used toflavoring material is between 2,500 and 10,000 ppm (0.25%-1.5%).

Any convenient method for incorporating the cyclic chemical compounds inthe tobacco product may be employed. Thus, the cyclic chemical compoundstaken alone or along with other flavoring additives may be dissolved ina suitable solvent such as ethanol, n-pentane, diethyl ether and/orother volatile organic solvents and the resulting solution may either besprayed on the cured, cased and blended tobacco material or the tobaccomaterial may be dipped into such solution. Under certain circumstances,a solution of the cyclic chemical compounds taken alone or taken furthertogether with other flavoring additives as set forth above, may beapplied by means of a suitable applicator such as a brush or roller onthe paper or leaf wrapper for the smoking product, or it may be appliedto the filter by either spraying to dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have the cyclic chemicalcompounds in excess of the amounts or concentrations above indicated sothat when blended with other tobaccos, the final product will have thepercentage within the indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded plastic domestic burley tobacco is spread with a 20% ethylalcohol solution of cyclic chemical compounds to provide a tobaccocomposition containing 800 ppm by weight of cyclic chemical compounds ona dry basis. Thereafter, the alcohol is removed by evaporation and thetobacco is manufactured into cigarettes by the usual techniques. Thecigarette when treated as indicated has a desired and pleasing aromawhich is detectable in the main and side streams when the cigarette issmoked. This aroma is described as being sweet, spicy, vanilla-like,woody, hay, and tobacco-like.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise, the cyclic chemical compounds of our inventioncan be incorporated with materials such as filter tip materials, seampaste, packaging materials and the like which are used along withtobacco to form a product adapted for smoking. Furthermore, the cyclicchemical compounds can be added to certain tobacco substitutes ofnatural or synthetic origin (e.g., dried lettuce leaves) and,accordingly, by the term "tobacco" as used throughout this specificationis meant any composition intended for human consumption by smoking orotherwise, whether composed of tobacco plant parts or substitutematerials or both.

One or more of the cyclic chemical compounds of our invention and one ormore auxiliary perfume ingredients, including, for example, alcohols,aldehydes, nitriles, esters, ketones other than the cyclic chemicalcompounds of our invention, cyclic esters other than the cyclic chemicalcompounds of our invention, synthetic essential oils, ethers other thanthe cyclic chemical compounds of our invention, and natural essentialoils may be admixed so that the combined odor of the individualcomponents produce a pleasant and desired fragrance, particularly andpreferably in floral fragrances. Such perfume compositions usuallycontain (a) the main note or the "bouquet" or foundation stone of thecomposition; (b) modifiers which round off and accompany the main note;(c) fixatives which include odorous substances which lend a particularnote to the perfume throughout all stages of evaporation and substanceswhich retard evaporation; and (d) topnotes which are usually low boilingfresh smelling materials.

In perfume compositions, it is the individual components whichcontribute particular olfactory characteristics, but the over-all effectof the perfume composition will be the sum of the effects of each of theingredients. Thus, the cyclic chemical compounds can be used to alterthe aroma characteristics of a perfume composition, for example byutilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of cyclic chemical compounds of our invention which will beeffective in perfume compositions depends on many factors, including theother ingredients, their amounts and the effects which are desired. Ithas been found that perfume compositions containing as little as 0.1% ofcyclic chemical compounds (e.g., 0.05%) can be used to impart sweet,fruity and green aroma nuances to soaps, cosmetics or other products.The amount employed can range up to 10% of the fragrance components andwill depend on considerations of cost, nature of the end product, theeffect desired on the finished product and the particular fragrancesought.

The cyclic chemical compounds of our invention are useful, taken aloneor in perfume compositions as olfactory components in detergents andsoaps, space odorants and deodorants, perfumes, colognes, toilet water,bath preparations, such as bath oils, and bath solids; hair preparation,such as lacquers, brilliantines, pomades and shampoos; cosmeticpreparations, such as creams, deodorants, hand lotions and sun screens;powders, such as talcs, dusting powders, face powders and the like. Whenused as an olfactory component, as little as 0.1% of the cyclic chemicalcompounds will suffice to impart a sweet, fruity and green aroma nuanceto fragrance formulations. Generally, no more than 3% of cyclic chemicalcompounds of our invention based on the ultimate end product is requiredin the perfume composition.

Insofar as perfumed articles are concerned the amount of cyclic chemicalcompound of our invention having the structure: ##STR29## wherein Z isbenzo or cyclohexano can vary from 0.01% by weight up to 3.0% by weightbased on the total weight of the perfumed article, that is based on thetotal weight of anionic, cationic or nonionic solid or liquid detergentbase; or fabric softener composition; or fabric softener article.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the cyclic chemicalcompounds of our invention. The vehicle can be a liquid such as anon-toxic alcohol, a non-toxic glycol, or the like. The carrier can alsobe an absorbent solid, such as a gum (e.g., gum arabic) or componentsfor encapsulating the composition (such as gelatin).

It will thus be apparent that cyclic chemical compounds can be utilizedto alter the sensory properties, particularly organoleptic properties,such as flavors and/or fragrances of a wide variety of consumablematerials.

The following examples are illustrative and the invention is to beconsidered to be restricted thereto only as indicated in the appendedclaims. These examples serve to illustrate processes for producing thecyclic chemical compounds useful in our invention and processes forusing the cyclic chemical compounds of our invention for theirorganoleptic properties.

All parts and percentages given are by weight unless otherwisespecified.

EXAMPLE I Preparation of 1,4-benzodioxan-2-one

Reaction: ##STR30##

Triethylamine (200 grams, 2 moles) is added dropwise to a solution of120 grams (1 mole) of catechol in 500 ml of toluene at 50° C.Bromoacetyl bromide (1 mole) is added over a one hour period withstirring and the reaction mass is heated to reflux. After one hour, themass is cooled and 500 mls of water are added thereto. The organic layeris washed twice with 25 ml of water. The toluene is removed underreduced pressure to afford 135 grams of a crude solid. Recrystallizationfrom ethanol affords 105 grams of colorless needles (m.p. 53°-55° C.)which is identified as 1,4-benzodioxan-2-one.

FIG. 1 shows the NMR spectrum of 1,4-benzodioxan-2-one.

FIG. 2 shows the IR spectrum of 1,4-benzodioxan-2-one.

EXAMPLE II Preparation of 1,4-benzodioxan-2-one

Reaction: ##STR31##

To a stirred solution of 120 grams of catechol and 10 grams of Aliquat®336 (brand of tricaprylmethylammonium chloride, of General MillsChemical Company of Minneapolis, Minnesota) at 80° C. is added ethylchloroacetate (87 grams, 1 mole) over a one hour period. The reactionmass is stirred for one hour and then cooled. 1000 ml of dilute (5%)hydrochloric acid is added with stirring. The aqueous layer isdiscarded. The organic layer is washed twice with a minimum amount ofwater. The toluene is distilled off under reduced pressure to afford 119grams of crude product. Recrystallization from ethanol afforded 92 gramsof 1,4-benzodioxan-2-one.

EXAMPLE III Preparation of trans-hexahydro-1,4-benzodioxan-2-one

Reaction: ##STR32##

To a slurry of 54 grams of 55% sodium hydride in 1000 mls of toluene isportionwise added 140 grams of trans-1,2-cyclohexanediol at 90° C. withconcommitant release of hydrogen. The resulting mass, containing themonosodium salt of trans-1,2-cyclohexanediol is stirred at 100° C. for30 minutes. Ethyl bromoacetate (203 grams) is added dropwise to thestirred reaction mass at 100° C. over a 30 minute period. After stirringfor 30 minutes, the mass is cooled to 20° C. Water (100 ml) is added andthe organic layer is distilled to afford 130 grams oftrans-hexahydro-1,4-benzodioxan-2-one. The product is purified bydistillation through a 1"×12" Goodloe® packed column to afford a semisolid (m.p. 20°-22° C., bp. 97° C. at 1.2 mm).

FIG. 3 is the NMR spectrum of fraction 4.

FIG. 4 is the IR spectrum of fraction 4.

EXAMPLE IV Perfume Composition

The following mixture is prepared:

    ______________________________________                                        Ingredient                Grams                                               ______________________________________                                        Benzyl acetate            50                                                  Rosewood Oil              100                                                 Cedarwood Oil             150                                                 Linalyl acetate           100                                                 α-Ionone            80                                                  Ethyl cinnamate           20                                                  Amyl cinnamic aldehyde    50                                                  Iso-eugenol               50                                                  Compound produced according to                                                Example I having the structure:                                                                         100                                                  ##STR33##                                                                    Methyl-3-isopropyl-6-methyl                                                   resorcylate               50                                                  Musk xylene               50                                                  Styrax resin              100                                                 ______________________________________                                    

The foregoing perfume formulation is an important part of chypreessence. The coumarin ordinarily used in this formulation has beenreplaced by the compound having the stucture: ##STR34## producedaccording to Example I or Example II. Themethyl-3-isopropyl-6-methyl-resorcylate is used as a replacement for theoakmoss. This perfume is incorporated into a soap at the 0.1% level. Anatural and distinctly oakmoss note is given to the soap.

EXAMPLE V Perfume Composition

The following mixture is prepared:

    ______________________________________                                        Ingredient                Grams                                               ______________________________________                                        Benzyl acetate            50                                                  Rosewood Oil              100                                                 Cedarwood Oil             150                                                 Linalyl acetate           100                                                 α-Ionone            80                                                  Ethyl cinnamate           20                                                  Amyl cinnamic aldehyde    50                                                  Iso-eugenol               50                                                  Compound produced according to                                                Example III having the structure:                                                                       100                                                  ##STR35##                                                                    Methyl-3-n-butyl-6-methyl                                                     resorcylate               200                                                 Musk xylene               50                                                  Styrax resin              100                                                 ______________________________________                                    

The foregoing perfume formulation is an important part of chypreessence. The coumarin ordinarily in this formulation has been replacedby the compound produced according to Example III having the structure:##STR36## The methyl-3-n-butyl-6-methyl resorcylate is used as areplacement for oakmoss. This perfume is incorporated into a soap at the0.1% level where a natural oakmoss aroma is imparted to said soap.

EXAMPLE VI Basic Walnut Formulation

The following basic walnut formulation is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Cyclotene             4                                                       Vanillin              1                                                       Butylisovalerate      2                                                       Benzaldehyde          6                                                       2,3-Diethyl pyrazine (10% in                                                  ethyl alcohol)        2                                                       Ethyl-2-methyl valerate                                                                             2                                                       gamma-Butyrolactone   20                                                      gamma-Hexenolactone   10                                                      2,4-Decadienal (0.1% in ethyl                                                 alcohol)              0.5                                                     2,4-Heptadienal (0.1% in ethyl                                                alcohol)              0.5                                                     Butylidene phthalide  2                                                       Propylene glycol USP  95                                                      ______________________________________                                    

The basic walnut formulation is divided into two parts. To the firstpart 0.5% by weight of the compound prepared according to Example Ihaving the structure: ##STR37## is added. Both flavors with and withoutthe additional material are compared at the rate of 100 parts permillion in water by a bench panel consisting of four people. The walnutflavor with the addition of the compound prepared according to Example 1having the structure: ##STR38## is considered to have characteristicfatty/oily walnut notes both in aroma and taste, with an additionalastringent taste and bitter notes which increase the mouthfeel of theflavor; whereas the flavor without the compound prepared according toExample I lacks the characteristic walnut flavor.

EXAMPLE VII Basic Walnut Formulation

The following basic walnut formulation is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Cyclotene             4                                                       Vanillin              1                                                       Butylisovalerate      2                                                       Benzaldehyde          6                                                       2,3-Diethyl pyrazine (10% in                                                  ethyl alcohol)        2                                                       Ethyl-2-methyl valerate                                                                             2                                                       gamma-Butyrolactone   20                                                      gamma-Hexenolactone   10                                                      2,4-Decadienal (0.1% in ethyl                                                 alcohol)              0.5                                                     2,4-Heptadienal (0.1% in ethyl                                                alcohol)              0.5                                                     Butylidene phthalide  2                                                       Propylene glycol USP  95                                                      ______________________________________                                    

The formulation is divided into two parts. To one of the parts 0.5% byweight of the compound having the structure: ##STR39## preparedaccording to Example III is added. To the second part of the basicwalnut formulation nothing else is added. Both formulations, with andwithout, the additional material are compared at the rate of 100 ppm inwater by a bench panel. All members of the bench panel prefer the walnutflavor with the addition of the compound prepared according to ExampleIII having the structure: ##STR40## the characteristic oily, walnutnotes and bitter mouthfeel effect are present.

EXAMPLE VIII Perfume Formulation

The following Fougere perfume formulation is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Oakmoss Absolute (50% in DEP)                                                                      2          2                                             Bergamot Oil         15         15                                            Lavender Oil         19         19                                            Citronellol          15         15                                            Patchouli Oil        4          4                                             Geranium Oil         5          5                                             gamma Methyl Ionone  15         15                                            Petitgrain Oil       2          2                                             Musk Ketone          8          8                                             Heliotropine         2          2                                             Clary Sage Oil       2          2                                             Amyl Salicylate      1          1                                             1,4-Benzodioxan-2-one (produced                                               according to Example I)                                                       having the structure:                                                                              10         --                                             ##STR41##                                                                    ______________________________________                                    

The compound of Example I gives surprising strength to this Fougereformulation and in addition acts as a fixative therefor. Addition of thecompound produced according to Example I greatly increases the aestheticqualities and gives the olfactory sensation of sweet, coumarin-likenotes.

EXAMPLE IX Tobacco Formulation

A tobacco mixture is produced by admixing the following ingredients:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           ______________________________________                                    

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Ethyl butyrate 0.05                                                           Ethyl valerate 0.05                                                           Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above stated tobacco flavor formulation is applied at the rate of0.1% to all of the cigarettes produced using the above tobaccoformulation. Half of the cigarettes are then treated with 500 or 1000ppm of the compound produced according to Example III having thestructure: ##STR42##

The control cigarettes not containing the compound produced according toExample III and the experimental cigarettes which contain the compoundproduced according to Example III are evaluated by paired comparison andthe results are as follows:

The experimental cigarettes are found to have more body and to be onsmoking more tobacco like, more aromatic, sweet, spicy, hay,tobacco-like.

The tobacco of the experimental cigarettes prior to smoking has a sweet,spicy, vanilla-like, woody, hay, tobacco-like aroma.

The product of Example III produced according to the process of ExampleIII enhances the tobacco-like taste and aroma of the blended cigaretteimparting to it woody, vanilla-like tobacco notes.

EXAMPLE X Perfumed Liquid Detergent

Concentrated liquid detergents with sweet, fruity, green, coumarin-likearoma nuances are prepared containing 0.10%, 0.15%, and 0.20% of thecompound produced according to Example III having the structure:##STR43##

They are prepared by adding and homogeneously mixing the appropriatequantity of hexahydro(trans)-1,4-benzodioxan-2-one prepared according toExample III in the liquid detergent. The detergents all possess a sweet,fruity, green, coumarin-like fragrance. The intensity increasing withgreater concentrations of hexahydro(trans)-1,4-benzodioxan-2-one.

EXAMPLE XI Preparation of Cologne and Handkerchief Perfume

Hexahydro(trans)-1,4-benzodioxan-2-one, prepared according to theprocess of Example III, is incorporated into cologne at concentrationsof 1.5%, 2.0%, 2.5%, 3.0%, 3.5% and 4.0% in 80%, 85% and 90% aqueousethanol; and into handkerchief perfumes at concentrations of 10%, 15%,20% and 25% (in 80%, 85%, 90% and 95% aqueous ethanol composition). Ineach of the compositions tested distinctive and definite sweet, fruity,green, coumarin-like aroma nuances are imparted to the colognes and tothe handkerchief perfumes.

EXAMPLE XII Preparation of Cologne and Handkerchief Perfume

The composition of Example IV is incorporated into colognes atconcentrations of 1.5%, 2.0%, 2.5%, 3.0%, 3.5% and 4.0% in 80%, 85% and90% aqueous ethanol; and into handkerchief perfumes at concentrations of15%, 20%, 25% and 30% (in 80%, 85%, 90% and 95% aqueous ethanol). Theuse of the composition of Example IV affords a distinct and definitestrong chypre aroma to the handkerchief perfume and cologne in eachcase.

EXAMPLE XIII Preparation of a Soap Composition

100 Grams of soap chips are mixed with 1 gram of 1,4-benzodioxan-2-oneproduced according to the process of Example II until a substantiallyhomogeneous composition is obtained. The perfumed soap compositionmanifests an excellent green, coumarin-like aroma.

EXAMPLE XIV Preparation of a Detergent Composition

A total of 100 grams of detergent phosphate powder is mixed with 0.15grams of 1,4-benzodioxan-2-one produced according to Example II until asubstantially homogeneous composition is obtained. The composition hasan excellent green, coumarin-like aroma.

EXAMPLE XV A. Powder Flavor Composition

20 Grams of the flavor composition of Example VI is emulsified in asolution containing 300 grams gum acacia and 700 grams of water. Theemulsion is spray dried with a Bowen Lab Model Dryer utilizing 260c.f.m. of air with an inlet temperature of 500° F. and an outlettemperature of 200° F., and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared:

    ______________________________________                                        Ingredient              Parts by Weight                                       ______________________________________                                        Liquid Walnut Flavor    20                                                    composition of Example VI                                                     (containing 1,4-benzodioxan-2-one)                                            Propylene Glycol        9                                                     Cab-O-Sil® M-5 (Brand of Silica                                                                   5.00                                                  produced by the Cabot Corp. of                                                125 High St., Boston, Mass.                                                   02110; Physical Properties:                                                   Surface Area: 200 m.sup.2 /gm                                                 Nominal particle size:                                                        0.012 microns; Density: 2.3 lbs/cu.ft.)                                       ______________________________________                                    

The Cab-O-Sil® is dispersed in the liquid walnut flavor composition ofExample VI with vigorous stirring thereby resulting in a viscous liquid.71 Parts by weight of the powder flavor composition of Part A supra isthen blended into said viscous liquid with stirring at 25° C. for aperiod of 30 minutes resulting in a dry, free flowing sustained releaseflavor powder.

EXAMPLE XVI

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts byweight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. 20 Parts by weight of the liquid flavor composition of ExampleVI is added to the solution which is then homogenized to form anemulsion having a particle size typically in the range of 2-5 microns.The material is kept at 120° F. under which conditions the gelatin willnot gel.

Coacervation is induced by adding, slowly and uniformly 40 parts byweight of a 20% aqueous solution of sodium sulphate. During coacervationof gelatin molecules are deposited uniformly about each oil droplet as anucleus.

Gelation is effected by pouring the heated coacervate mixture into 1000parts by weight of a 7% aqueous solution of sodium sulphate at 65° F.The resulting gelled coacervate may be filtered and washed with water attemperatures below the melting point of gelatin, to remove the salt.

Hardening of the filter cake, in this example, is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove the residual formaldehyde.

EXAMPLE XVII Chewing Gum

100 Parts by weight of chicle are mixed with 4 parts by weight of theflavor prepared in accordance with Example XV. 300 Parts of sucrose and100 parts of corn syrup are added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing, the chewing gum has a pleasant long lastingsweet, fruity, walnut flavor.

EXAMPLE XVIII Chewing Gum

100 Parts by weight of chicle are mixed with 18 parts by weight of theflavor prepared in accordance with Example XVI. 300 Parts of sucrose and100 parts of corn syrup are then added. Mixing is effected in a ribbonblender with jacketed side walls of the type manufactured by the BakerPerkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inchin width and 0.1 inches in thickness. The strips are cut into lengths of3 inches each. On chewing the chewing gum has a pleasant long lastingsweet, fruity, walnut flavor.

EXAMPLE XIX Toothpaste Formulation

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight  Ingredients                                                  ______________________________________                                        Group "A"                                                                     30.200           Glycerin                                                     15.325           Distilled Water                                               .100            Sodium Benzoate                                               .125            Saccharin Sodium                                              .400            Stannous Fluoride                                            Group "B"                                                                     12.500           Calcium Carbonate                                            37.200           Dicalcium Phosphate                                                           (Dihydrate)                                                  Group "C"                                                                     2.000            Sodium N-Lauroyl Sarcosi-                                                     nate (foaming agent)                                         Group "D"                                                                     1.200            Flavor Material of                                                            Example XV                                                   100.00 (Total)                                                                ______________________________________                                    

Procedure:

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogenous gel.

3. The powders of Group "B" are added to the gel, while mixing until ahomogenous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodiumn-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completedpaste is then transferred to a three roller mill and then homogenized,and finally tubed.

The resulting toothpaste when used in a normal tooth-brushing procedureyields a pleasant sweet, walnut flavor, of constant strong intensitythroughout said procedure (1-1.5 minutes).

EXAMPLE XX Chewable Vitamin Tablets

The flavor material produced according to the process of Example XVI isadded to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kgwhich Chewable Vitamin Tablet Formulation is prepared as follows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                        Ingredients           Gms/1000 Tablets                                        ______________________________________                                        Vitamin C (ascorbic acid as                                                   ascorbic acid-sodium ascor-                                                   bate mixture 1:1      70.0                                                    Vitamin B.sub.1 (thiamine mononi-                                             trate) as Rocoat® thiamine                                                monomitrate 33 1/3%                                                           (Hoffman La Roche)    4.0                                                     Vitamin B.sub.2 (riboflavin) as                                               Rocoat® riboflavin 33 1/3%                                                                      5.0                                                     Vitamin B.sub.6 (pyridoxine hydro-                                            chloride) as Rocoat® pyrido-                                              xine hydrochloride 33 1/3%                                                                          4.0                                                     Niacinamide as Rocoat®                                                    niacinamide 33 1/3%   33.0                                                    Calcium pantothenate  11.5                                                    Vitamin B.sub.12 (cyanocobalamin)                                             as Merck 0.1% in gelatin                                                                            3.5                                                     Vitamin E (dl-alpha tocopheryl                                                acetate) as dry Vitamin E                                                     acetate 33 1/3% Roche 6.6                                                     d-Biotin              0.044                                                   Certified lake color  5.0                                                     Flavor of Example XVI (as indicated above)                                    Sweetener sodium saccharin                                                                          1.0                                                     Magnesium stearate lubricant                                                                        10.0                                                    Mannitol q.s. to make 500.0                                                   ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 g dry Vitamin A Acetate and 0.6 gVitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong sweet, walnut flavor for a period of 12 minutes.

EXAMPLE XXI Chewing Tobacco

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15%Pennsylvania leaf) the following casing is sprayed at a rate of 30%:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Corn Syrup             60                                                     Licorice               10                                                     Glycerine              20                                                     Fig Juice              4.6                                                    Prune Juice            5                                                      Flavor Material of Example XV                                                                        0.4                                                    ______________________________________                                    

The resultant product is redried to a moisture content of 20%. Onchewing, this tobacco has an excellent substantially consistent,long-lasting sweet, green, walnut (20 minutes) nuance in conjunctionwith the main fruity tobacco note.

EXAMPLE XXII Preparation of a Solid Detergent Composition

A detergent is prepared from the following ingredients according toExample I of Canadian Pat. No. 1,007,948:

    ______________________________________                                                           Percent by Weight                                          ______________________________________                                        "Neodol 45-11" (a C.sub.14 --C.sub.15                                                              12                                                       alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                   Sodium carbonate     55                                                       Sodium citrate       20                                                       Sodium sulfate, water                                                                              q.s.                                                     brighteners                                                                   ______________________________________                                    

This detergent is a "phosphate-free" detergent. A total of 100 grams ofthis detergent is admixed with 0.15 grams of the chypre base perfume ofExample IV. The detergent has an excellent green, chypre aroma.

EXAMPLE XXIII Perfumed Liquid Detergent

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976) with green, chypre aromas are prepared containing 0.50%of the perfume formulation of Example IV. They are prepared by addingand homogeneously mixing the appropriate quantity of perfume formulationin the liquid detergent. The detergents all possess green, chypre aromanuances, the intensity of each of the foregoing characteristicsincreasing with greater concentrations of perfume formulations in thedetergent.

EXAMPLE XXIV

Utilizing the procedure of Example I of column 15 of U.S. Pat. No.3,632,396, a nonwoven cloth substrate useful as a dryer-addedfabric-softening article of manufacture is prepared wherein thesubstrate, the substrate coating and the outer coating and the perfumingmaterial are as follows:

1. a water "dissolvable" paper ("Dissolvo Paper").

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. An outer coating having the following formulation (m.p. about 150°F.):

57 percent C₂₀₋₂₂ HAPS

22 percent isopropyl alcohol

20 percent antistatic agent

1 percent of the bicyclic compound prepared according to Example IIIhaving the structure: ##STR44##

The compound having the structure: ##STR45## prepared according toExample III gives rise to an excellent sweet, green, coumarin-likearoma.

A fabric softening composition prepared as set forth above having theabove aroma characteristics essentially consists of a substrate having aweight of about 3 grams per 100 square inches, a substrate coating ofabout 1.85 grams per 100 square inches of substrate and an outer coatingof about 1.4 grams per 100 square inches of substrate, thereby providinga total aromatized substrate and outer coating weight ratio of about 1:1by weight of the substrate. The aroma as set forth above is imparted ina pleasant manner to the head space in the dryer on operation thereofusing the said dryer added fabric softening nonwoven fabric.

What is claimed is:
 1. A process for augmenting or enhancing the aromaor taste of a smoking tobacco comprising the step of adding to smokingtobacco an organoleptic property augmenting or enhancing quantity of acyclic chemical compound having the structure: ##STR46## wherein Z isbenzo or cyclohexano.
 2. A smoking tobacco article comprising a shapedbody of tobacco, a wrapper in contact with said shaped body of tobacco,a filter in contact with said shaped body of tobacco and intimately incontact with either of said wrapper or said shaped tobacco body or saidfilter at least one cyclic chemical compound having the structure:##STR47## wherein Z represents benzo or cyclohexano.